Composition and method for making a proppant

ABSTRACT

The present invention relates to proppants which can be used to prop open subterranean formation fractions. Proppant formulations are further disclosed which use one or more proppants of the present invention. Methods to prop open subterranean formation fractions are further disclosed. In addition, other uses for the proppants of the present invention are further disclosed, as well as methods of making the proppants.

This application claims the benefit under 35 U.S.C. §119(e) of priorU.S. Provisional Patent Application No. 60/649,594 filed Feb. 4, 2005,which is incorporated in its entirety by reference herein.

BACKGROUND OF THE INVENTION

Recognition that the macroscopic properties of materials depend not onlyon their chemical composition, but also on the size, shape and structurehas spawned investigations into the control of these parameters forvarious materials. In this regard, the fabrication of uniform hollowspheres has recently gained much interest. Hollow capsules withnanometer and micrometer dimensions offer a diverse range of potentialapplications, including utilization as encapsulants for the controlledrelease of a variety of substances, such as drugs, dyes, proteins, andcosmetics. When used as fillers for coatings, composites, insulatingmaterials or pigments, hollow spheres provide advantages over thetraditional solid particles because of their associated low densities.Hollow spheres may also be used in applications as diverse ashierarchical filtration membranes and proppants to prop open fracturesin subterranean formations.

Ceramic proppants are widely used as propping agents to maintainpermeability in oil and gas formations. Conventional proppants offeredfor sale exhibit exceptional crush strength but also extreme density.Typical densities of ceramic proppants exceed 100 pounds per cubic foot.Proppants are materials pumped into oil or gas wells at extreme pressurein a carrier solution (typically brine) during the fracturing process.Once the pumping-induced pressure is removed, proppants “prop” openfractures in the rock formation and thus preclude the fracture fromclosing. As a result, the amount of formation surface area exposed tothe well bore is increased, enhancing recovery rates. Proppants also addmechanical strength to the formation and thus help maintain flow ratesover time. Three grades of proppants are typically employed: sand,resin-coated sand and ceramic proppants. Proppants are principally usedin gas wells, but do find application in oil wells.

Relevant quality parameters include: particle density (low density isdesirable), crush strength and hardness, particle size (value depends onformation type), particle size distribution (tight distributions aredesirable), particle shape (spherical shape is desired), pore sizedistribution (tight distributions are desirable), surface smoothness,corrosion resistance, temperature stability, and hydrophilicity(hydro-neutral to phobic is desired).

Ceramic proppants dominate sand and resin-coated sand on the criticaldimensions of crush strength and hardness. They offer some benefit interms of maximum achievable particle size, corrosion and temperaturecapability. Extensive theoretical modeling and practical case experiencesuggest that conventional ceramic proppants offer compelling benefitsrelative to sand or resin-coated sand for most formations.Ceramic-driven flow rate and recovery improvements of 20% or morerelative to conventional sand solutions are not uncommon.

Ceramic proppants were initially developed for use in deep wells (e.g.,those deeper than 7,500 feet) where sand's crush strength is inadequate.In an attempt to expand their addressable market, ceramic proppantmanufacturers have introduced products focused on wells of intermediatedepth.

Resin-coated sands offer a number of advantages relative to conventionalsands. First, resin coated sands exhibit higher crush strength thanuncoated sand given that resin-coating disperses load stresses over awider area. Second, resin-coated sands are “tacky” and thus exhibitreduced “proppant flow-back” relative to conventional sand proppants(e.g. the proppant stays in the formation better). Third, resin coatingstypically increase sphericity and roundness thereby reducing flowresistance through the proppant pack.

Ceramics are typically employed in wells of intermediate to deep depth.Shallow wells typically employ sand or no proppant. As will be describedin later sections, shallow “water fracs'” represent a potential marketroughly equivalent to the current ceramic market in terms of ceramicmarket size.

With a combined annual production of over 30 million tons, the oxidesand hydroxides of aluminum are undoubtedly among the most industriallyimportant chemicals (K. Wefers and C. Misra, “Oxides and Hydroxides ofAluminum.” Alcoa Laboratories, 1987). Their uses include: precursors forthe production of aluminum metal, catalysts and absorbents; structuralceramic materials; reinforcing agents for plastics and rubbers, antacidsand binders for the pharmaceutical industry; and as low dielectric lossinsulators in the electronics industry. With such a diverse range ofapplications, it is unsurprising that much research has been focused ondeveloping and understanding methods for the preparation of thesematerials.

Traditional ceramic processing involves three basic steps generallyreferred to as powder processing, shape forming, and densification,often with a final mechanical finishing step. Although several steps maybe energy intensive, the most direct environmental impact arises fromthe shape-forming process where various binders, solvents, and otherpotentially toxic agents are added to form and stabilize a solid(“green”) body. In addition to any innate health risk associated withthe chemical processing, these agents are subsequently removed ingaseous form by direct evaporation or pyrolysis. In many cast-parts, theliquid solvent alone consists of over 50% of the initial volume ofmaterial. The component chemicals listed, with relative per percentage,in Table 1 are essentially mixed to a slurry, cast, then dried andfired. All solvents and additives must be removed as gaseous productsvia evaporation or pyrolysis. TABLE 1 Composition of a non aqueoustape-casting alumina slurry Function Composition Volume % Powder Alumina27 Solvent 1,1,1-Trichloroethylene/Ethyl Alcohol 58 DeflocculentMenhaden Oil 1.8 Binder Polyvinyl Butyrol 4.4 Plasticizer PolyethyleneGlycol/Octyl Phthalate 8.8

Whereas the traditional sintering process is used primarily for themanufacture of dense parts, the solution-gelation process has beenapplied industrially primarily for the production of porous materialsand coatings. Solution-gelation involves a four-stage process:dispersion; gelation; drying; firing. A stable liquid dispersion or solof the colloidal ceramic precursor is initially formed in a solvent withappropriate additives. By change in concentration (aging) or pH, thedispersion is polymerized to form a solid dispersion or gel. The excessliquid is removed from this gel by drying and the final ceramic isformed by firing the gel at higher temperatures.

The common solution-gelation route to aluminum oxides employs aluminumhydroxide or hydroxide-based material as the solid colloid, the secondphase being water and/or an organic solvent. Aluminum hydroxide gelshave traditionally been prepared by the neutralization of a concentratedaluminum salt solution; however, the strong interactions of the freshlyprecipitated alumina gels with ions from the precursors solutions makesit difficult to prepare these gels in pure form. To avoid thiscomplication alumina gels may be prepared from the hydrolysis ofaluminum alkoxides, Al(OR)₃ (Eq. 1).

Although this method was originally reported by Adkins in 1922 (A.Adkins, J. Am. Chem. Soc. 1922, 44, 2175), it was not until the 1970'swhen it was shown that transparent ceramic bodies can be obtained by thepyrolysis of suitable alumina gels, that interest increasedsignificantly (B. E. Yoldas, J. Mat. Sci. 1975, 10, 1856).

The exact composition of the gel in commercial systems is ordinarilyproprietary, however, a typical composition can include an aluminumcompound, a mineral acid and a complexing agent to inhibit prematureprecipitation of the gel, e.g., Table 2. The aluminum compound wastraditionally assumed to be the direct precursor to pseudo-boehmite.However, the gel is now known to consist of aluminum-oxygenmacromolecular species with a boehmite-like core: alumoxanes. TABLE 2Typical composition of an alumina sol-gel for slipcast filter membranesFunction Composition Boehmite Precursor ASB [aluminum sec-butoxide,Al(OC₄H₉)₃] Electrolyte HNO₃ 0.07 mole/mole ASB Complexing agentglycerol ca. 10 wt. %

The replacement of 1,1,1-trichloroethylene (TCE) as a solvent in thetraditional ceramic process must be regarded as a high priority forlimiting environmental pollution. Due to its wide spread use as asolvent in industrial processes, TCE has become one of the most commonlyfound contaminants in ground waters and surface waters. Concentrationsrange from parts per billion to hundreds of milligrams per liter. TheUnited States Environmental Protection Agency (USEPA) included TCE onits 1991 list of 17 high-priority toxic chemicals targeted for sourcereduction. The 1988 releases of TCE reported under the voluntary rightto know provisions of Superfund Amendments and Reauthorization Act(SARA) totaled to 190.5 million pounds.

The plasticizers, binders, and alcohols used in the process present anumber of potential environmental impacts associated with the release ofcombustion products during firing of the ceramics, and the need torecycle or discharge alcohols which, in the case of discharge towaterways, may exert high biological oxygen demands in the receivingcommunities.

Ceramic ultrafiltration (UF) and nanofiltration (NF) membranes have beenfabricated by the sol-gel process in which a thin membrane film isdeposited, typically by a slip-cast procedure, on an underlying poroussupport. This is typically achieved by hydrolysis of Al, Ti, Zr or othermetal compounds to form a gelatinous hydroxide at a slightly elevatedtemperature and high pH. In the case of alumina membranes, this firststep may be carried out with 2-butanol or iso-propanol. After removingthe alcohol, the precipitated material is acidified, typically usingnitric acid, to produce a colloidal suspension. By controlling theextent of aggregation in the colloidal sol, membranes of variablepermeability may be produced. The aggregation of colloidal particles inthe sol is controlled by adjusting the solution chemistry to influencethe diffuse layer interactions between particles or throughultrasonification. Alternatively, a sol gel can be employed, which isthen applied to a porous support. While this procedure offers greatercontrol over membrane pore size than does the metal precipitation route,it is nonetheless a difficult process to manipulate. In both cases,plasticizers and binders are added to improve the properties of the slipcast solution. Once the film has been applied it is dried to preventcracking and then sintered at high temperature.

The principal environmental results arising from the sol-gel process arethose associated with use of strong acids, plasticizers, binders, andsolvents. Depending on the firing conditions, variable amounts oforganic materials such as binders and plasticizers may be released ascombustion products. NOx's may also be produced from residual nitricacid in the off-gas. Moreover, acids and solvents must be recycled ordisposed of. Energy consumption in the process entails “upstream”environmental emissions associated with the production of that energy.

The aluminum-based sol-gels formed during the hydrolysis of aluminumcompounds belong to a general class of compounds: alumoxanes. Alumoxaneswere first reported in 1958 and have since been prepared with a widevariety of substituents on aluminum. The structure of alumoxanes wasproposed to consist of linear (I) or cyclic (II) chains (S.Pasynkiewicz, Polyhedron, 1990, 9, 429). Recent work has redefined thestructural view of alumoxanes, and shown that they are not chains butthree dimensional cage compounds (A. W. Apblett, A. C. Warren, and A. R.Barron, Chem. Mater., 1992, 4, 167; C. C. Landry, J. A. Davis, A. W.Apblett, and A. R. Barron, J. Mater. Chem., 1993, 3, 597). For example,siloxy-alumoxanes, [Al(O)(OH)x(OSiR3)1−x]n, consist of analuminum-oxygen core structure (III) analogous to that found in themineral boehmite, [Al(O)(OH)]n, with a siloxide substituted periphery.

Precursor sol-gels are traditionally prepared via the hydrolysis ofaluminum compounds (Eq. 1). This “bottom-up” approach of reacting smallinorganic molecules to form oligomeric and polymeric materials has metwith varied success, due to the difficulties in controlling the reactionconditions, and therefore the stoichiometries, solubility, andprocessability, of the resulting gel. It would thus be desirable toprepare alumoxanes in a one-pot bench-top synthesis from readilyavailable, and commercially viable, starting materials, which wouldprovide control over the products.

In the siloxy-alumoxanes, the “organic” unit itself contains aluminum,i.e., IV. Thus, in order to prepare the siloxy-alumoxane similar tothose previously reported the anionic moiety, the “ligand”[Al(OH)₂(OSiR₃)₂]⁻, would be used as a bridging group; adding this unitwould clearly present a significant synthetic challenge. However, thecarboxylate-alumoxanes represent a more realistic synthetic target sincethe carboxylate anion, [RCO₂]⁻, is an isoelectronic and structuralanalog of the organic periphery found in siloxy-alumoxanes (IV and V).Based upon this rational, a “top-down” approach has been developed basedupon the reaction of boehmite, [Al(O)(OH)]n, with carboxylic acids, Eq.2 (Landry, C. C.; Pappé, N.; Mason, M. R.; Apblett, A. W.; Tyler, A. N.;MacInnes, A. N.; Barron, A. R., J. Mater. Chem. 1995, 5, 331).

The carboxylate-alumoxane materials prepared from the reaction ofboehmite and carboxylic acids are air and water stable materials and arevery processable. The soluble carboxylate-alumoxanes can be dip-coated,spin coated, and spray-coated onto various substrates. The physicalproperties of the alumoxanes are highly dependent on the identity of thealkyl substituents, R, and range from insoluble crystalline powders topowders that readily form solutions or gels in hydrocarbon solventsand/or water. The alumoxanes are indefinitely stable under ambientconditions, and are adaptable to a wide range of processing techniques.Given the advantages observed for the application of carboxylatealumoxanes, e.g., the low price of boehmite ($1 kg⁻¹) and theavailability of an almost infinite range of carboxylic acids make thesespecies ideal as precursors for ternary and doped aluminum oxides. Thealumoxanes can be easily converted to γ-Al₂O₃ upon mild thermolysis (A.W. Apblett, C. C. Landry, M. R. Mason, and A. R. Barron, Mat. Res. Soc.,Symp. Proc., 1992, 249, 75).

SUMMARY OF THE INVENTION

A feature of the present invention is to provide a proppant havingsuitable crush strength and/or buoyancy as shown by specific gravity.

A further invention of the present invention is to provide a proppantthat can overcome one or more of the disadvantages described above.

The present invention relates to a proppant comprising a templatematerial and a shell on the template material, wherein the shellcomprises a ceramic material or oxide thereof or a metal oxide. Thetemplate material can be a hollow sphere and can be a single particle,such as a cenosphere.

The present invention further relates to a proppant having a surfacethat comprises a ceramic material or oxide thereof or a metal oxide,wherein the surface has an average grain size of 1 micron or less. Otheraverage grain sizes are possible. The surface can have a maximum grainsize, as well as a tight distribution with respect to the grain sizes.

The present invention further relates to a method to prop opensubterranean formation fractions using one or more proppants, which arepreferably contained in proppant formulations.

The present invention further relates to methods of making the variousproppants of the present invention. For instance, one method includescoating a template material with a formulation comprising a ceramicmaterial or oxide thereof or a metal oxide to form a shell around thetemplate and then hardening the shell, such as by sintering orcalcining. Other methods are further described.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are intended to provide a further explanation of the presentinvention, as claimed.

The accompanying figures, which are incorporated in and constitute apart of this application, illustrate various embodiments of the presentinvention and, together with the description, serve to explain theprinciples of the present invention.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic showing an embodiment of a proppant of the presentinvention showing a substrate (A) with the coating (B). The substrate(A) may be chosen from a group including, but not limited to, ceramic,natural material, shell, nut, or other materials. The coating (B) can bechosen from a group including, but not limited to, ceramic, ceramicprecursor, polymer, resin, or a nanoparticle reinforced polymer or ananoparticle reinforced resin.

FIG. 2 shows a schematic of a proppant of the present invention showinga hollow substrate (C) with the coating (B). The substrate (C) may bechosen from a group including, but not limited to, ceramic, naturalmaterial, shell, nut, or other described in the claims. The coating (B)can be chosen from a group including, but not limited to, ceramic,ceramic precursor, polymer, resin, or a nanoparticle reinforced polymeror a nanoparticle reinforced resin.

FIG. 3 shows a schematic of the reaction or conversion of the coating(B) and substrate (A) to form a mixed phase or new phase material (D).

FIG. 4 is an SEM image of pre-expanded polystyrene with 1 coat of a 10%acetate-alumoxane nanoparticle solution and heated to 220° C. for 1hour.

FIG. 5 is a SEM image of cenosphere with a coating of 10% acetatealumoxane nanoparticle solution heated to 1000° C. for 1 hour.

FIGS. 6-11 are SEM microphotographs of several embodiments of thepresent invention.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

The materials of the present invention when used as proppants coulddominate current proppant solutions on all relevant quality dimensions.The methods of this invention are aimed at the fabrication of proppantsthat preferably exhibit neutral buoyancy, high crush strength, highsphericity, narrow size distribution, and/or high smoothness. Thesematerials have the ability to materially reduce and/or possiblyeliminate the need to employ expensive and reservoirpermeability-destroying polymer carrier gels.

Equally important, the optimal shape, size, size distribution, pore sizedistribution, and/or surface smoothness properties of the presentinvention suggest that flow resistance through the proppant pack couldbe reduced, such as by more than 50%. Neutral buoyancy enhances proppanttransport deep into the formation increasing the amount of fracture-areapropped thereby increasing the mechanical strength of the reservoir. Dueto the above issues, proppants of the present invention can achievesubstantially increased flow rates and/or enhanced hydrocarbon recovery.The low-cost of the present invention's preferred nanoparticles, and thereduced material requirements (on a per pound basis) are advantages ofthe present invention's preferred proppants. The low density of thepresent invention's proppants may enable reductions in transportationcosts in certain situations.

The proppants of the present invention present oil and gas producerswith one or more of the following benefits: improved flow rates,improved productive life of wells, improved ability to design hydraulicfractures, and/or reduced environmental impact. The proppants of thepresent invention are designed to improve flow rates, eliminating ormaterially reducing the use of permeability destroying polymer gels,and/or reducing pressure drop through the proppant pack, and/or theability to reduce the amount of water trapped between proppants therebyincreasing hydrocarbon “flow area.”

The high density of conventional ceramic proppants and sands (roughly100 lb/cu.ft.) inhibit their transport inside fractures. High densitycauses proppants to “settle out” when pumped thereby minimizing theirefficacy. To maintain dense proppants in solution, expensive polymergels are typically mixed with the carrier solution (e.g. completionfluid). Once suspended in a gelled completion fluid, proppant transportis considerably enhanced.

Polymer gels are extremely difficult to de-cross link, however. As aresult, the gel becomes trapped downhole, coats the fracture, andthereby reduces reservoir permeability. Gel-related reservoirpermeability “damage factors” can range from 40% to more than 80%depending on formation type.

The neutral buoyancy property that can be exhibited by the proppants ofthe present invention preferably eliminates or greatly reduces the needto employ permeability destroying polymer gels as they naturally stay insuspension.

Equally important, the shape and surface properties of the proppants ofthe present invention preferably reduce the pressure drop through theproppant pack. As a result, flow rates should increase. Theoreticalmodeling of the non-linear non-darcy flow effects (reduced beta factor)associated with the proppants of the present invention show that thisbenefit could be significant—perhaps more than a 50% reduction inproppant pack flow resistance. Key details include improved sphericityand roundness, improved surface smoothness, and/or near-monodispersesize distribution.

In one or more embodiments, the proppants of the present invention aredesigned to improve reservoir flow rates by changing the hydrophilicproperties of the proppants themselves. The hydrophilic nature ofcurrent proppants causes water to be trapped in the pore spaces betweenproppants. If this water could be removed, flow rates would beincreased.

The use of extreme pressure, polymer gels, and/or exotic completionfluids to place ceramic proppants into formations adversely impacts themechanical strength of the reservoir and shortens its economic life.Proppants of the present invention preferably enable the use of simplercompletion fluids and possibly less (or slower) destructive pumping.Thus, reservoirs packed with neutrally buoyant proppants preferablyexhibit improved mechanical strength/permeability and thus increasedeconomic life.

More importantly, enhanced proppant transport enabled by neutralbuoyancy preferably enable the placement of the proppant of the presentinvention in areas that were heretofore impossible, or at least verydifficult to prop. As a result, the mechanical strength of the formationis preferably improved, preferably reducing decline rates over time.This benefit could be of significant importance—especially within “waterfracs” where the ability to place proppants is extremely limited.

If neutrally buoyant proppants are employed, water (fresh to heavybrines) may be used in place of more exotic completion fluids. The useof simpler completion fluids would reduce or eliminate the need toemploy de-crossing linking agents. Further, increased use ofenvironmentally friendly proppants may reduce the need to employ otherenvironmentally damaging completion techniques such as flashingformations with hydrochloric acid.

In addition to fresh water, salt water and brines, or synthetic fluidsare sometimes used in placing proppants to the desired locations. Theseare of particular importance for deep wells.

In the present invention a range of approaches for the synthesis andfabrication of proppants with designed buoyancy are disclosed. Theproppants are designed such that the material properties are such thatthe proppant preferably has neutral, positive, or negative buoyancy inthe medium chosen for pumping the proppant to its desired location inthe subterranean formation.

In the present invention, the proppant can be either solid throughout orhollow within the proppant to control buoyancy. In the presentinvention, a solid proppant is defined as an object that does notcontain a void space in the center, although a porous material would besuitable. A fully dense material is not a requirement of solid. A hollowmaterial is defined as a object that has a void space inside with adefined size and shape.

In the present invention the proppant can be made from a ceramic, apolymer, or mixture thereof. The proppant can be made fromnanoparticles. The proppant can be a composite or combination ofceramic, polymer and other materials. Although not required it isunderstood that a ceramic may include oxides such as aluminum oxides(alumina) or mixed metal aluminum oxides (aluminates).

The strength properties for a proppant can be dependent on theapplication. It is intended that a crush strength of 4000 psi or higheris desirable. However, for specific applications, crush-strengths ofgreater than 9000 psi or greater than 12000 psi are desirable. Othercrush strengths below or above these ranges are possible.

The optimum size of the proppant can also be dependent on the particularapplication. Part of the present invention is that it is possible todesign various proppant sizes. Sizes (e.g., particle diameters) may varyfrom 10 μm to 10,000 μm. The particle diameter can be in the range offrom 50 μm to 2,000 μm.

Although the proppant can be made from a single-phase material or can bemade from a multi-phase system, such as from a two phase system thatcomprises a substrate (or template) and a second phase. A summary ofexemplary templates and substrates is shown in Table 3.

The substrate or template may be an inorganic material such as a ceramicor glass. Specifically, the ceramic can be an oxide such as aluminumoxides (alumina) as well as mixed metal aluminum oxides such as metalaluminates containing calcium, yttrium, titanium, lanthanum, barium,and/or silicon in addition to aluminum. In order to make variablebuoyant proppants, it is preferable to use a ceramic cenosphere orsimilar glass-like hollow sphere as the substrate or template.

Alternatively, the substrate may be a polymer or organic molecule orsurfactant. Although not limited as such, the polymer may be chosen frompolystyrene, latex, polybutadiene, polyethylene, polypropylene andchemically related polymers. The polymer can be a naturally occurringmaterial such as a peptide or protein.

Alternatively, the substrate can be a naturally occurring materialchosen from plant or tree material, such as plant seeds, crushed nuts,whole nuts, plant pips, cells, coffee grinds, or food products.

In a two-phase system, the second phase can coat the supporting ortemplate first phase, or infiltrates the supporting or template firstphase, or reacts with the supporting or template first phase.

The second phase can be a polymer, such as an epoxide, polyolefin, orpolymethacrylate. Furthermore, a nanopartcle material such as analumoxane optionally containing chemical functional groups that allowfor reaction with the polymer can reinforce the polymer. Suitablechemical functional groups or substituents include, but are not limitedto, hydroxides, amines, carboxylates or olefins.

The second phase can also be a ceramic or glass. The ceramic can be anoxide, such as aluminum oxide called alumina, or a mixed metal oxide ofaluminum called an aluminate, a silicate, or an aluminosilicate, such asmullite or cordierite. The aluminate or ceramic may contain magnesium,calcium, yttrium, titanium, lanthanum, barium, and/or silicon. Theceramic may be formed from a nanoparticle precursor such as analumoxane. Alumoxanes can be chemically functionalized aluminum oxidenanoparticles with surface groups including those derived fromcarboxylic acids such as acetate, methoxyacetate, methoxyethoxyacetate,methoxyethoxyethoxyacetate, lysine, and stearate, and the like.

The designed proppant can be suspended in a liquid phase. The liquidphase may make the proppant more easy to transport to a drill site.Transportation may be by rail transport, road or ship, or any otherappropriate method, depending on geography and economic conditions. Inaddition to transport to the drill site, the suspended mixture ispreferably pumpable or otherwise transportable down the well to asubterranean formation and placed such as to allow the flow ofhydrocarbons out of the formation.

Specific methods for designing proppants with specific buoyancy,strength, size, and/or other desirable properties are summarized below.

A proppant particle with controlled buoyancy and crush strength used toprop open subterranean formation fractures can be made from a naturallyoccurring substrate coated with an organic polymer or resin coatingpreferably containing a nanoparticle reinforcement. The naturallyoccurring substrate can be chosen from the following group: crushed nutshells, plant seeds, coffee grinds, plant pips, or other food products.The organic polymer or resin can be chosen from the following group:epoxide resin, polyethylene, polystyrene, or polyaramide. Thenanoparticle reinforcement can be of various types, but is preferably acarboxylate alumoxane in which the carboxylate alumoxane optionally hasone or more types of chemical functional groups that can react orotherwise interact with the polymer resin and/or also allow for thealumoxane to be miscible with the polymer. Proppants of this design maybe made by suspending a substrate material in a suitable solvent, addingthe polymer, resin or resin components, adding the nanoparticle,allowing the resin and nanoparticle mixture to coat the substratematerial, and drying the coated particle. The nanoparticle and resincomponents can be pre-mixed before addition to the substrate, and asolvent or other components can be a component of the resin or polymer.

A proppant particle with controlled buoyancy and crush strength used toprop open subterranean formation fractures can be made from a ceramicsubstrate and an organic polymer or resin coating. The ceramic substrateor template can be a non-porous or porous particle and can be a solid orhollow particle. It is preferable that the particle is a hollowspherical particle such as a cenosphere or similar product. Cenospherescan be commercially produced ceramic or glass hollow spheres that aremade as side products in various industrial processes. The organicpolymer or resin can be chosen from the following group: epoxide resin,polyethylene, polystyrene, or polyaramide. Proppants of this design maybe made by suspending a substrate material in a suitable solvent, addingthe polymer, resin or resin components, allowing the resin to coat thesubstrate material, and drying the coated particle. It is possible touse a solvent to facilitate the coating process. An improved version ofthis proppant can be prepared by the addition of nanoparticles forreinforcement, such as an alumoxane optionally with chemical functionalgroups that react and/or allow miscibility with the polymer resin. Analternative method of controlling the properties of the proppant is toadd a linker group to the surface of the ceramic substrate that canreact with the organic polymer or resin coating.

A proppant particle with controlled buoyancy and/or crush strength usedto prop open subterranean formation fractures can be made from a ceramicsubstrate, a ceramic coating, or infiltration. The ceramic substrate ortemplate is preferably spherical and hollow such as a cenosphere orsimilar material. However, any suitable substrate that provides theresulting properties of the proppant may be used. The ceramic coating orinfiltration can be an oxide, for instance, an oxide of aluminum or amixed metal oxide of aluminum. A proppant of this type may be preparedby coating of a spherical template with a ceramic precursor solution,drying the coated ceramic particle, and heating the coated ceramicparticle to a temperature sufficient to form ceramic sphere of desiredporosity and hardness. The ceramic precursor may be a nanoparticle suchas an alumoxane, or a sol-gel precursor. Proppants of this type may beprepared by suspending the ceramic substrate in a suitable solvent,adding a ceramic precursor, allowing the ceramic precursor to coat theceramic substrate, drying the coated ceramic particle, and heating thecoated ceramic particle to a temperature sufficient to form ceramicspheres of desired porosity and hardness. TABLE 3 Possible Templates forproppants Food and food Plants and products minerals Waste Other Coffee,Soils, Slag (steel, coke) a) Polypropylene, Milk, Bauxite, Silicas b)Glass Beads Whey, Cellulose, (diatomaceous earth, c) Surfactants/Animal/Fish Guargum, diatomite, kesselgur, Detergents Eggs, Algae,Popped Perlite, d) Polystyrene Nuts, Lignin, Vermiculate), e) BacteriaSmall corn Poppy Seeds, Fly ash (coke), f) Erasers pieces. Mustard SeedsRust, g) Soap Sawdust Wood flour, Rape Seeds Gypsum h) macrolite GrainHusks Plankton (fertilizer), (corn, maize, Pieces of Rubber (tires),mailo, capher, sponge Spent FCC sorgum). Fur/Hair, Kohl catalyst, RabiSeeds Spent Motor Oil Used adsorbents Flue gas filter cakes from bags inbaghouses cenospheres

In the present invention, in one or more embodiments, the inventionrelates to a proppant used to prop open subterranean formation fractionscomprising a particle or particles with controlled buoyancy and/or crushstrength. The controlled buoyancy can be a negative buoyancy, a neutralbuoyancy, or a positive buoyancy in the medium chosen for pumping theproppant to its desired location in the subterranean formation. Themedium chosen for pumping the proppant can be any desired medium capableof transporting the proppant to its desired location including, but notlimited to a gas and/or liquid, like aqueous solutions, such as water,brine solutions, and/or synthetic solutions. Any of the proppants of thepresent invention can have a crush strength sufficient for serving as aproppant to prop open subterranean formation fractures. For instance,the crush strength can be 3,000 psi or greater, greater than 4000 psi,greater than 9000 psi, or greater than 12000 psi. Suitable crushstrength ranges can be from about 3000 psi to about 15000 psi, or fromabout 5000 psi to about 15000 psi, and the like.

The proppants of the present invention can comprise a single particle ormultiple particles and can be a solid, partially hollow, or completelyhollow in the interior of the particle. The particle can be spherical,nearly spherical, oblong in shape (or any combination thereof) or haveother shapes suitable for purposes of being a proppant.

The proppant can have any particle size. For instance, the proppant canhave a particle diameter size of from about 1 nm to 1 cm or a diameterin the range of from about 1 micron to about 1 mm, or a diameter of fromabout 10 microns to about 10000 microns, or a diameter of from about1000 microns to about 2000 microns. Other particle sizes can be used.Further, the particle sizes as measured by their diameter can be abovethe numerical ranges provided herein or below the numerical rangesprovided herein.

In one or more embodiments of the present invention, the particlecomprising the proppant can be or can contain a ceramic material. Theceramic material can comprise an oxide such as an oxide of aluminum. Theceramic material can comprise an aluminate. For instance, the aluminatecan be an aluminate of calcium, yttrium, titanium, lanthanum, barium,silicon, any combinations thereof, and other elements that can formaluminates.

In the present invention, the particle(s) forming the proppant cancomprise a substrate or template and a second phase, such as a coatingon the substrate or template. The substrate or template can be a polymeror surfactant or ceramic material. The polymer, for instance, can be anythermoplastic or thermoset polymer, or naturally occurring polymer. Forinstance, the polymer can be a polystyrene, a latex, or polyalkylene,such as a polyethylene or polypropylene. The polymer can be apolybutadiene, or related polymers or derivatives of any of thesepolymers. The polymer can be a naturally occurring material or cancontain a naturally occurring material. For instance, the naturallyoccurring material can be a peptide or protein, or both.

With respect to the substrate or template, the substrate or template canbe a naturally occurring material or can contain a naturally occurringmaterial. For instance, the naturally occurring material can be a plantmaterial or tree material. For instance, the naturally occurringmaterial can be a plant seed, a crushed nut, whole nut, plant pip, cell,coffee grind, or food products, or any combination thereof. The ceramicmaterial can comprise a cenosphere.

The second phase or coating, or shell can coat the template orsubstrate. The second phase or template can infiltrate the template orsubstrate. Further, or in the alternative, the second phase or shell orcoating can react with the substrate or template, or a portion thereof.

The second phase, coating, or shell, can comprise one or more polymerssuch as a thermoplastic or thermoset polymer(s). Examples include, butare not limited to, an oxide, polyolefin, polymethacrylate, and thelike. The coating, shell, or second phase can optionally be reinforcedby nanoparticles. The nanoparticle material can be any type of materialcapable of acting as a reinforcement material. Examples include, but arenot limited to, ceramics, oxides, and the like. Specific examplesinclude, but are not limited to, alumoxane. The alumoxane can optionallycontain one or more chemical functional groups that are on thealumoxane. These chemical functional groups can permit, facilitate, orotherwise permit reaction with a polymer that also forms the coating orshell, or the polymer that may be present in the template or substrate.Examples of substituents that may be on the nanoparticles, such as thealumoxane, include, but are not limited to, hydroxides, amines,carboxylates, olefins, and/or other reactive groups, such as alkylgroups, aromatic groups, and the like.

The coating or shell or second phase can be or contain a ceramicmaterial(s), such as an oxide(s). Specific examples include, but are notlimited to, an oxide(s) of aluminum. The ceramic can be an aluminate oralumina. For instance, the aluminate can be an aluminate of calcium,yttrium, titanium, lanthanum, barium, silicon, or any combinationthereof, or can contain other elements. The material forming the coatingor shell can be initially in the form of a nanoparticle such as analumoxane. The alumoxane can be acetate, methoxyacetate,methoxyethoxyacetate, methoxyethoxyethoxyacetate, lysine, stearate, orany combination thereof.

In one or more embodiments of the present invention, the proppant can besuspended in a suitable liquid phase. The liquid phase is generally onethat permits transport to a location for use, such as a well site orsubterranean formation. For instance, the subterranean formation can beone where proppants are used to improve or contribute to the flow ofhydrocarbons, natural gas, or other raw materials out of thesubterranean formation. In another embodiment of the present invention,the present invention relates to a well site or subterranean formationcontaining one or more proppants of the present invention.

In one embodiment of the present invention, the proppant whichpreferably has controlled buoyancy and/or crush strength has a naturallyoccurring substrate or template with an organic polymer or resin coatingon the template or substrate and wherein the organic polymer or resincoating contains nanoparticles, preferably for reinforcement purposes.As specific examples, but non-limiting examples, the naturally occurringsubstrate can be a crushed nut, cell, plant seed, coffee grind, planttip, or food product. The organic polymer or resin coating, forinstance, can be an epoxy resin, polyethylene, polystyrene, orpolyaramide, or other thermoplastic or thermoset polymers. Thenanoparticle can be an alumoxane, such as an carboxylate alumoxane orother ceramic material. The alumoxane can have one or more chemicalfunctional groups that are capable of reacting with the organic polymeror resin coating. The functional groups can optionally allow the ceramicmaterials, such as alumoxane, to be miscible with the polymer or resincoating. The crush strength of this proppant can be as describedearlier. The proppant can have a diameter as described earlier or can bea diameter in the size range of from about 25 to about 2000 microns.Other diameter size ranges are possible.

In the present invention, the template or substrate can be a ceramicmaterial with an organic polymer or resin coating. The ceramic substratecan be a porous particle, substantially non-porous particle, or anon-porous particle. The ceramic template or substrate can be spherical.The ceramic substrate can be a hollow particle. For instance, theceramic substrate can be a cenosphere. The organic polymer or resincoating can be as described above. The crush strength can be the same asdescribed above. The diameter can be the same as described earlier.Optionally, the proppant can have nanoparticles for reinforcement valueor other reasons. The nanoparticle can be in the polymer or resincoating. The nanoparticle can be the same as described earlier.

In another embodiment, the proppant can have a substrate or templatecontaining or made from one or more ceramic material(s). A linker groupcan be located on the template or substrate. A shell or coatingcontaining a polymer containing a resin coating can be located aroundthis template or substrate having the linker group. More than one typeof linker group can be used. The linker group, in at least oneembodiment, permits bonding between the substrate or template and thecoating. The linker group can be a coupling agent. The coupling agentcan be of the type used with metal oxides.

In another embodiment, the proppant can have a substrate or templatethat comprises a ceramic material and further has a coating or shellthat comprises a ceramic material that can be the same or different fromthe template material. The template or substrate and the shell orcoating can have the same characteristics and parameters as describedabove for the other embodiments, such as shape, crush strength,buoyancy, and the like. Preferably, the ceramic substrate or template isa cenosphere and the ceramic coating or shell is an oxide, such as anoxide of aluminum or aluminate, a silicate, or an aluminosilicate. Otherexamples include, but are not limited to, shells that contain silicon,yttrium, magnesium, titanium, calcium, or any combinations thereof.

The proppants of the present invention can be made a number of ways. Forinstance, the substrate material can be suspended in a suitable solventand then the material forming the shell or coating can be added to thesolvent containing the suspended substrate material. Optionally,nanoparticles can be added. The coating material, such as the polymer orresin, as well as the nanoparticle(s) present as a mixture can then coatthe substrate material. Afterwards, the coated particle is dried usingconventional drying techniques such as an oven or the like. The optionalpresence of nanoparticles can optional react with the coating material,such as the polymer or resin. Furthermore, if nanoparticles are used,the nanoparticles can be added separately or can be pre-mixed with thecoating components, such as the resin or polymer, prior to beingintroduced to the suspension of substrate material. The solvent that isused to suspend the substrate material can be part of or present withthe polymer or resin coating materials. Furthermore, the coatingmaterials can optionally cross link during the coating process toperform a cross-linked coating on the substrate or template.

As another option, if a linkage molecule or material is used, thelinkage molecule can be reacted with the substrate or template prior tobeing suspended in a solvent, or after the substrate material issuspended in a solvent. The linkage molecule optionally reacts with thesubstrate or template material and optionally reacts with the coating orshell material such as the resin or polymer. Again, nanoparticles can beadded at any point of this process.

In another method of making one or more types of proppants of thepresent invention, a template or substrate material can be coated, suchas with a precursor solution such as a ceramic containing precursorsolution. The coated template material can then be dried andsubsequently heated to a temperature to form a densified shell, forinstance, having desirable porosity or hardness, or both. Preferably,the material is in the shape of a sphere. In this embodiment, theprecursor solution preferably comprises nanoparticles such as ceramicnanoparticles. For instance, ceramic particles can be alumoxane. Theprecursor solution can be in the form of a sol-gel. For instance, thesol-gel can contain aluminum as well as other elements. The template orsubstrate can be a hollow particle and/or can be spherical in shape. Thecoating that coats the ceramic template can optionally react with thesubstrate, for instance, during the heating step.

In another embodiment of the present invention, the proppant can beobtained by suspending a substrate, such as a ceramic substrate in asuitable solvent such as water or other aqueous solutions. The ceramicprecursor which coats the template or substrate can be added. Theceramic precursor then coats the substrate or template and then thecoated particle such as the coated ceramic particle can then be driedand subjected to heating to a temperature to form a densified materialhaving desirable porosity and/or hardness. The types of materials,characteristics, and parameters of the starting materials and finishedcoated particles as described above apply equally here in theirentirety.

In a more preferred embodiment, a solid or hollow alumina,aluminosilicate, or metal aluminate ceramic sphere is obtained bycoating a spherical template with an alumoxane solution or metal dopedalumoxane and then subsequent application of heat to convert this sphereto alumina, aluminosilicate, or a metal aluminate. The alumoxane cancomprise acetate-alumoxane. The spherical template preferably has adiameter in the size range of from about 25 to 2000 microns. The solidor hollow spherical templates can be ceramic or can be polystyrene orother polymeric materials. Even more preferably, the templates arecenospheres or synthetically produced microspheres such as thoseproduced from a blowing process or a drop tower process. In oneembodiment, the solid or hollow spherical templates remain in tactduring the conversion process to alumina, aluminosilicate, or metalaluminate. In one or more embodiments, the solid or hollow sphericaltemplates pyrolize, decompose, or are otherwise removed during theconversion process to alumina, aluminosilicate, or metal aluminate. Thewall thickness can be of any desirable thickness. For instance, the wallthickness can be in a range of from about 25 to about 2000 microns. Asan option, the surface of the formed alumina, aluminosilicate, or metalaluminate sphere can be functionalized with a chemical moiety orchemical material, such as an organic ligand, like a surfactant, and canprovide surface wetting properties which can assist in allowingadditional ceramic precursor, which is the same or different from theearlier coating, to be applied. Then, additional heat conversion canoccur to form the second or multiple coating or shell on the alreadycoated particle.

In another embodiment, the solid or spherical templates can be firstcoated with a resin or polymer and cured and then an alumoxane precursoror other similar type of precursor can be subsequently coated onto theparticle followed by heat conversion to form a sphere comprised of anouter alumina, aluminosilicate, or metal aluminate shell or similar typeof metal containing coating. This resin coating or polymer coating canpyrolize, decompose, or otherwise be removed during the conversionprocess. The coating used to coat the particles such as a solution ofalumoxane nanoparticles can contain, for instance, from about 0.5 toabout 20% alumoxane by weight of the coating solution. Other weights arepossible and permissible. The coating of the particles can occur such asby dipped coating, pan, Muller mixing, or fluid bed coating.

With respect to the polymers or resins that can be used to coat theparticles, these polymers include, but are not limited to, epoxies,polyurethanes, phenols, ureas, melamine formaldehyde, furans, syntheticrubber, natural rubber, polyester resins, and the like.

The proppants of the present invention while preferably used to propopen subterranean formation fractions, can be used in othertechnologies, such as an additive for cement or an additive forpolymers, or other materials that harden, or would benefit. Theproppants of the present invention can also be used as encapsulateddelivery systems for drugs, chemicals, and the like.

In another method of making the proppants of the present invention, acolloidal suspension containing polymeric beads can be suspended in anysolution such as an aqueous solution of a nanostructured coatingmaterial. The beads can then be covered with a nanostructured coatedmaterial to create a ceramic. The beads can then be dried andsubsequently heated to a first temperature which is sufficient toconvert the nanostructured coating material to a ceramic coating, suchas a densified coating. The temperature is preferably not sufficient todecompose the polymeric beads. Then, the polymeric beads can bedissolved, such as in a solvent, and extracted from the ceramic coating.Afterwards, the material can then be heated to a second temperature toform a hollow ceramic sphere of the desired porosity and/or strength.The nanostructure coating material can be as described above earlier,such as titania, alumina, chromium, molybdenum, yttrium, zirconium, orthe like, or any combination thereof. The nanostructure coating materialdispersed in the solution can be achieved using a sol-gel method,controlled flow cavitation, PVD-CVD, flame, plasma, high energy ballmilling, or mechanomade milling processes. The nanostructure coatingmedia can be a solution, such as alcohol, liquid hydrocarbon, orcombinations thereof.

In the present invention, the strength of the particle can be controlledby varying the wall thickness, the evenness of the wall thickness, thetype of nanoparticles used, or any combination thereof. Further, thesize of the particle can be controlled by varying the type, size, or anycombination thereof of the template used. The template can have a sizeof from about 1 nm to about 3000 microns.

In the present invention, in one or more embodiments, the templatematerial can be selected from wax, surfactant-derived liquid beads,seeds, shells, nuts, grain husks, grains, soils, powdered, ground, orcrushed agglomerates of wood products, powdered, ground, or crushedagglomerates of ceramic material, powdered, ground, crushed, or rolledorganics, silicas (glass beads), whey, cellulose, fly ash, animal eggs,rust, soap, bacteria, algae, and rubber.

More particular examples or seeds are rape seed, a poppy seed, a mustardseed, a kohl rabbi seed, a pea seed, a pepper seed, a pumpkin seed, anoil seed, a watermelon seed, an apple seed, a banana seed, an orangeseed, a tomato seed, a pear seed, a corn seed.

More particular examples of shells are walnut shell, peanut shell,pasticcio shell, or an acorn shell. More specific examples of grainhusks include, corn, maize, mailo, capher, or sorgum. Another way tocoat a particle in the present invention, can be with spray drying,rolling, casting, thermolysis, and the like.

Examples of powdered agglomerates of organic material include powderedmilk, animal waste, unprocessed polymeric resins, animal hair, plantmaterial, and the like. Examples of animal eggs include, but are notlimited to, fish, chicken, snake, lizard, bird eggs, and the like.Examples of cellulose templates include, but are not limited to algae,flower, plankton, ground cellulose such as saw dust, hay, or othergrasses, and the like. In general, the material coated can have a sizeof from about 100 to about 10,000 microns.

While the various embodiments of the present invention have beendescribed in considerable detail, the following provides additionaldetails regarding various embodiments of the present invention. It isnoted that the above disclosure of the proppants, methods of making, anduses applies equally to the following disclosure of various embodimentsof the present invention. Equally so, the following disclosure alsoapplies to the above embodiments of the present invention. Thesedisclosures are not exclusive of each other.

In one or more embodiments of the present invention, the presentinvention relates to a proppant comprising a template material and ashell on the template material. The shell can comprise a ceramicmaterial or oxide thereof or a metal oxide. The shell can contain one ormore types of ceramic material, or oxides thereof, or metal oxides, orany combinations thereof. The metal oxide can be a mixed metal oxide ora combination of metal oxides.

The template material can be porous, non-porous, or substantiallynon-porous. For purposes of the present invention, a substantiallynon-porous material is a material that is preferably at least 80%non-porous in its entirety, more preferably, at least 90% non-porous.The template material can be a hollow sphere or it can be a closed foamnetwork, and/or can be a non-composite material. A non-compositematerial, for purposes of the present invention is a material that isnot a collection of particles which are bound together by some binder orother adhesive mechanism. The template material of the present inventioncan be a single particle. In other words, the present invention canrelate to a plurality of proppants, wherein each proppant can consistsof a single particle. In one or more embodiments of the presentinvention, the template material can be a cenosphere or a syntheticmicrosphere such as one produced from a blowing process or a drop towerprocess.

Though optional, the template material can have a crush strength of 5000psi or less, 3000 psi or less, or 1000 psi or less. In the alternative,the template material can have a high crush strength such as 3000 psi ormore, such as from about 5000 psi to 10,000 psi. For purposes of thepresent invention, crush strength is determined according to APIPractice 60 (2^(nd) Ed. December 1995). In one or more embodiments ofthe present invention, the template material having a low crush strengthcan be used to provide a means for a coating to be applied in order toform a shell wherein the shell can contribute a majority, if not a highmajority, of the crush strength of the overall proppant.

The template material can optionally have voids and these voids can bestrictly on the surface of the template material or strictly in theinterior of the template material or in both locations. As describeearlier, the shell can be sintered which can form a densified materialwhich preferably has high crush strength. For instance, the shell cancomprise sintered nanoparticles. These nanoparticles can be quite small,such as on the order of 0.1 nm up to 150 nm or higher with respect toprimary particle size. The nanoparticles can comprise primary particlesalone, agglomerates alone, or a combination of primary particles andagglomerates. For instance, the primary particles can have an averageparticle size of from about 1 nm to about 150 nm and the agglomeratescan have an average particle size of from about 10 nm to about 350 mm.The weight ratio of primary particles to agglomerates can be 1:9 to 9:1or any ratio in between. Other particle size ranges above and belowthese ranges can be used for purposes of the present invention. Theshell of the proppant can have an average grain size of about 10 micronsor less. The shell of the present invention can have an average grainsize of 1 micron or less. The shell of the proppant of the presentinvention can have an average grain size of from 0.1 micron to 0.5micron. In any of these embodiments, the maximum grain size can be 1micron. It is to be understood that maximum size refers to the highestgrain size existing with respect to measured grain sizes. With respectto any of these embodiments, as an option, at least 90% of all grainsizes can be within the range of 0.1 to 0.6 micron.

With respect to the shell, the shell can further comprise additionalcomponents used to contribute one or more properties to the shell orproppant. For instance, the shell can further comprise at least onesintering aid, glassy phase formation agent, grain growth inhibitor,ceramic strengthening agent, crystallization control agent, and/or phaseformation control agent, or any combination thereof. It is to beunderstood that more than one of any one of these components can bepresent and any combination can be present. For instance, two or moresintering aids can be present, and so on. There is no limit to thecombination of various agents or the number of different agents used.Generally, one or more of these additional agents or aids can includethe presence of yttrium, zirconium, iron, magnesium, alumina, bismuth,lanthanum, silicon, calcium, cerium, one or more silicates, one or moreborates, or one or more oxides thereof, or any combination thereof.These particular aids or agents are known to those skilled in the art.For instance, a sintering aid will assist in permitting uniform andconsistent sintering of the ceramic material or oxide. A glassy phaseformation agent, such as a silicate, generally enhances sintering byforming a viscous liquid phase upon heating in the sintering process. Agrain growth inhibitor will assist in controlling the overall size ofthe grain. A ceramic strengthening agent will provide the ability tostrengthen the overall crush strength of the shell. A crystallizationcontrol agent will assist in achieving the desired crystalline phase ofthe shell upon heat treatment such as sintering or calcining. Forinstance, a crystallization control agent can assist in ensuring that adesirable phase is formed such as an alpha aluminum oxide. A phaseformation control agent is the same or similar to a crystallizationcontrol agent, but can also include assisting in achieving one or moreamorphous phases (in addition to crystalline phases), or combinationsthereof. The various aids and/or agents can be present in any amounteffective to achieve the purposes described above. For instance, the aidand/or agents can be present in an amount of from about 0.1% to about 5%by weight of the overall weight of the shell. The shell(s) can compriseone or more crystalline phases or one or more glassy phases orcombinations thereof.

The template material can be a synthetic ceramic microsphere such as oneproduced from a blowing process or a drop tower process or can be acenosphere such as a hollow cenosphere. The template material can be afly ash particle or particles and can be a particle or particles derivedfrom fly ash. In more general terms, the template material can be ahollow spherical particle. The template material can be a precipitatorfly ash. The template material can be a blown hollow sphere. In otherwords, the hollow sphere can be naturally occurring or synthetic or canbe a combination.

In one or more embodiments of the present invention, the shell can besubstantially non-porous. For instance, substantially non-porous meansthat at least 90% of the surface of the shell is non-porous.

The shell can be substantially uniform in thickness around the entireouter surface of the template material. For instance, the thickness ofthe shell can be substantially uniform in thickness by not varying inthickness by more than 20% or more preferably by not varying more than10% in overall thickness around the entire circumference of the shell.The shell can be non-continuous or continuous. Continuous, for purposesof the present invention means that the shell entirely encapsulates orcovers the template material within the shell. Preferably, the shellfully-encapsulates the template material.

With respect to the shell and the interaction of the shell and thetemplate material, the shell can essentially be a physical coating onthe template material and not react with the template material.Alternatively, the shell can react with one or more portions of thetemplate material such as by chemically bonding to the templatematerial. This chemical bonding may be ionic or covalent or both. As analternative, the shell or portion thereof can diffuse, infiltrate,and/or impregnate at least a portion of the template material. Asanother alternative, the shell or at least a portion thereof can adsorbor absorb onto the template material or a portion thereof.

With respect to the outer surface of the template material and theshell, the shell can be in direct contact with the outer surface of thetemplate material. Alternatively, one or more intermediate layers can bepresent in between the outer surface of the template material and theinner surface of the shell. The intermediate layer or layers can be ofany material, such as a polymer, resin, ceramic material, oxidematerial, or the like.

The proppants of the present application can, for instance, have aspecific gravity of from about 0.6 g/cc to about 2.5 g/cc. The specificgravity can be from about 1.0 g/cc to about 1.3 g/cc or can be from abut0.9 g/cc to about 1.5 g/cc. Other specific gravities above and belowthese ranges can be obtained.

The proppant can have any of the crush strengths mentioned above, suchas 3000 psi or greater, 5000 psi to 10,000 psi, 10,000 psi to 15,000psi, as well as crush strengths above and below these ranges.

The shell of the proppant can have a wall thickness of any amount, suchas 5 microns to about 150 microns or about 15 microns to about 120microns. This wall thickness can be the combined wall thickness for twoor more shell coatings forming the shell or can be the wall thicknessfor one shell coating.

As stated, the proppant can be spherical, oblong, nearly spherical, orany other shapes. For instance, the proppant can be spherical and have asphericity of at least 0.7, at least 0.8, or at least 0.9. The term“spherical” can refer to roundness and sphericity on the Krumbein andSloss Chart by visually grading 10 to 20 randomly selected particles.

In one or more embodiments of the present invention, the proppant can bea spray-coated shell. The shell(s) of the proppants can be formulated byone coating or multiple coatings. More than one shell can be present inlayered constructions. The coatings can be the same or different fromeach other.

In one or more embodiments of the present invention, the shell cancomprise at least alumina, aluminosilicate, aluminate, or silicate. Forinstance, the alumina, aluminate, or silicate can contain calcium,yttrium, magnesium, titanium, lanthanum, barium, and/or silicon, or anycombination thereof. One or more rare earth metals or oxides thereof canbe present.

The template material can be from a naturally occurring material asdescribed earlier. The naturally occurring material can be seed, plantproducts, food products, and the like. Specific examples have beendescribed earlier.

The proppants of the present invention, for instance, can be made bycoating a template material with a formulation comprising a ceramicmaterial or oxide thereof or metal oxide to form a shell around thetemplate and then this formulation can be sintered to create thesintered shell having a densified structure. The shell preferably has amicrocrystalline structure. The sintering can occur at any temperatureto achieve densification of the ceramic material or oxide thereof ofmetal oxide such as from about 800° C. to about 1700° C. Generally,sintering occurs by ramping up to the temperature. The sinteringtemperature is the temperature in the oven or sintering device. Asstated, the coating of the template material can be achieved by spraycoating. For instance, in creating the shell, a non-alpha aluminum oxidecan be coated onto a template material and then upon sintering, form analpha-aluminum oxide coating. The formulation can be in the form of aslurry comprising the ceramic material or oxide thereof or metal oxidealong with a carrier such as a liquid carrier. When spray coating, aspray coating chamber can be used such as a spray coater from VectorCorporation, Model MLF.01. The formulation can be introduced as anatomized spray and the template material is suspended in air within thechamber during the coating of the template material. Ranges for keyparameters for the spray coating process include: Air temperature:40°-90° C., Airflow: 90-150 liters per minute, Nozzle Air Setting: 10-25psi. After coating, the sintering can occur.

With respect to the sintering, it is preferred that the sintering issufficient to densify the ceramic material or oxide thereof or metaloxide so as to form a continuous coating. The formulation can compriseat least one acid, surfactant, suspension aid, sintering aid, graingrowth inhibitor, glassy phase formation agent, ceramic strengtheningagent, crystallization control agent, and/or phase formation controlagent, or any combination thereof. One or more of these agents can bepresent. Again, as stated above, more than one type of the same agentcan be used such as more than one type of acid, more than one type ofsurfactant, more than one type of sintering agent, and so on. The amountof these agents can be any amount sufficient to accomplish the desiredpurposes such as from about 0.1% to about 5% by weight of the weight ofthe final shell.

As stated above, the present invention further relates to a proppantformulation comprising one or more proppants of the present inventionwith a carrier. The carrier can be a liquid or gas or both. The carriercan be water, brine, hydrocarbons, oil, crude oil, gel, foam, or anycombination thereof. The weight ratio of carrier to proppant can be from10,000:1 to 1:10,000 or any ratio in between, and preferably 0.001 lbproppant/gallon fluid to 10 lb proppant/gallon fluid.

In a more preferred example, the proppant can have the followingcharacteristics:

(a) an overall diameter of from about 90 microns to about 1,600 microns;

(b) spherical;

(c) said shell is substantially non-porous;

(d) said proppant has a crush strength of about 3,000 psi or greater;

(e) said coating has a wall thickness of from about 15 to about 120microns;

(f) said proppant has a specific gravity of from about 0.9 to about 1.5g/cc; and

(g) said template material is a hollow sphere.

Preferably, in this embodiment, the template material is a cenosphere oran aluminate, or a sintered aluminum oxide. The template materialpreferably has a crush strength of less than 3000 psi or less than 1000psi. The shell is preferably an alpha aluminum oxide coating.

For the proppants of the present invention, the shell can compriseMullite, Cordierite, or both. In one embodiment of the presentinvention, the formulation that is applied onto the template materialcan be prepared by peptizing Boehmite or other ceramic or oxidematerials with at least one acid (e.g., acetic acid) to form a sol-gelformulation comprising alumoxane. The formulation can be a slurrycomprising alumoxane along with a carrier such as a liquid carrier. Theslurry can contain one or more sintering aids, grain growth inhibitors,ceramic strengthening agents, glassy phase formation agents,crystallization control agents, and/or phase formation control agents,which can comprise yttrium, zirconium, iron, magnesium, alumina,bismuth, silicon, lanthanum, calcium, cerium, silicates, and/or borates,or oxides thereof, or any combination thereof.

As an additional embodiment, the present invention can comprise asurface that comprises a ceramic material or an oxide thereof or metaloxide wherein the surface (e.g., polycrystalline surface) has an averagegrain size of 1 micron or less. The average grain size can be about 0.5micron or less. The average grain size can be from about 0.1 micron toabout 0.5 micron. The surface having this desirable grain size can bepart of a coating, shell, or can be the core of a proppant or can be aproppant solid particle or hollow particle. The surface can have amaximum grain size of 5 microns or less, such as 1 micron. Further, thesurface can have grain sizes such that at least 90% of all grain sizesare within the range of from about 0.1 to about 0.6 micron. The proppantcan have a crush strength of 3000 psi or greater or can have any of thecrush strengths discussed above, such as 5000 psi or more or 10,000 psior more, including from about 5000 psi to about 15,000 psi. The ceramicmaterial in this proppant can further contain yttrium, zirconium, iron,magnesium, alumina, bismuth, lanthanum, silicon, calcium, cerium,silicates, and/or borates, or oxides thereof or any combination thereof.The proppants can contain one or more of sintering aid, glassy phaseformation agent, grain growth inhibitor, ceramic strengthening agent,crystallization control agent, or phase formation control agent, or anycombination thereof. The proppant formulation can contain the proppantalong with a carrier such as a liquid carrier or a gas carrier.

With respect to this embodiment, a template material is optional. Theproppant can be completely solid, partially hollow, or completelyhollow, such as a hollow sphere. If a template material is present, anyone of the template materials identified above can be used.

In all embodiments of the present invention, one or more proppants ofthe present invention can be used alone or in a formulation to prop opensubterranean formation fractions by introducing the proppant formulationinto the subterranean formation such as by pumping or other introductionmeans known to those skilled in the art. An example of a well completionoperation using a treating fluid containing proppants or particles isgravel packing. In gravel packing operations, particles referred to inthe art as gravel are carried to a subterranean producing zone in whicha gravel pack is to be placed by a hydrocarbon or water carrying fluid.That is, the particles are suspended in the carrier fluid which can beviscosified and the carrier fluid is pumped into the subterraneanproducing zone in which a gravel pack is to be placed. Once theparticles are placed in the zone, the treating fluid leaks off into thesubterranean zone and/or is returned to the surface. The gravel packproduced functions as a filter to separate formation solids fromproduced fluids while permitting the produced fluids to flow into andthrough the well bore. An example of a production stimulation treatmentutilizing a treating fluid having particles suspended therein ishydraulic fracturing. That is, a treating fluid, referred to in the artas a fracturing fluid, is pumped through a well bore into a subterraneanzone to be stimulated at a rate and pressure such that fractures areformed and extended into the subterranean zone. At least a portion ofthe fracturing fluid carries particles, referred to in the art asproppant particles into the formed fractures. The particles aredeposited in the fractures and the fracturing fluid leaks off into thesubterranean zone and/or is returned to the surface. The particlesfunction to prevent the formed fractures from closing whereby conductivechannels are formed through which produced fluids can flow to the wellbore.

While the term proppant has been used to identify the preferred use ofthe materials of the present invention, it is to be understood that thematerials of the present invention can be used in other applications,such as medical applications, filtration, polymeric applications,catalysts, rubber applications, filler applications, drug delivery,pharmaceutical applications, and the like.

U.S. Pat. Nos. 4,547,468; 6,632,527 B1; 4,493,875; 5,212,143; 4,777,154;4,637,990; 4,671,909; 5,397,759; 5,225,123; 4,743,545; 4,415,512;4,303,432; 4,303,433; 4,303,431; 4,303,730; and 4,303,736 relating tothe use of proppants, conventional components, formulations, and thelike can be used with the proppants of the present invention, and areincorporated in their entirety by reference herein. The processesdescribed in AMERICAN CERAMIC SOCIETY BULLETIN, Vol. 85, No. 1, January2006, and U.S. Pat. Nos. 6,528,446; 4,725,390; 6,197,073; 5,472,648;5,420,086; and 5,183,493, and U.S. Patent Application Publication No.2004/0012105 can be used herein and is incorporated in its entiretyherein. The proppant can be a synthetic proppant, like a syntheticcenosphere template, with any shell.

Sol-gel routes to forming monoliths or films, such as thicker than about1 micron, can suffer from severe cracking or warping during the dryingor gel consolidation process. Low solids-weight loadings result in largevolumetric shrinkage during the drying process. Furthermore, crackingcan be the result of relief of differential capillary stresses acrossthe dimensions of the gel or film as drying and shrinkage occur. Totalcapillary stress present in the film can be a function of particle size,and decreases as particle size increases. As a result, films ormonoliths formed from larger particle sizes can have a decreasedtendency to incur cracking stresses during the shrinkage and dryingprocess.

In a peptized formulation, such as a boehmite gel formulation, ablending of boehmite particles of varying dispersed size (e.g., 90%large, aggregated crystallites and 10% small, single crystallites)results in a lower number density of pores, as well as larger size ofpore in the corresponding dried gel, thereby reducing drying stress.Thus, tailoring the particle size and blend of primary particles in thesol-gel formulation can confer control over crack formation for a givendrying process. The particles have varying dispersed sizes in thesol-gel stage, but examination of the microstructure of the dried gelfragments reveals that only crystallites are distinct from one anotherin the green packing. This shows that the small particles uniformly fillthe interstices of the larger particles, resulting in a well-structuredgreen film.

The present invention will be further clarified by the followingexamples, which are intended to be exemplary of the present invention.

EXAMPLES

An aqueous acetate-alumoxane solution was prepared according to themethod described in Chem. Mater. 9 (1997) 2418 by R. L. Callender, C. J.Harlan, N. M. Shapiro, C. D. Jones, D. L. Callahan, M. R. Wiesner, R.Cook, and A. R. Barron, incorporated in its entirety by referenceherein. The aqueous solution was degassed before use. The aqueousacetate-alumoxane solution mentioned above, in the solution range of0.5-20 weight percent, was degassed before use. Cenosphere templates inthe size range of 100-600 micron were coated with the alumoxanesolutions as described in the examples below.

In Example 1, spherical polystyrene template beads were coated with thealumoxane solution, ranging from 0.5-20 weight percent alumoxanenanoparticles. The template spheres were submerged in the solution atroom temperature. The solution was then drained, and the spheres placedin a ceramic crucible, which were allowed to dry under controlledconditions. The preferred conditions were at room temperature for 48hours under 70% relative humidity. These dried, coated spheres were thenagitated, and recoated two more times as stated above to achieve auniform coating, and to maximize their sphericity. The spheres were thenheated to 180° C. for 40 minutes to burn off organics and to set thealumina shell. After cooling to room temperature, the spheres werecoated again with the alumoxane solution, dried, and reheated to 180°C., as stated above, which resulted in a thickening of the aluminashell. The templated alumina spheres were then sintered at 1200° C. for1 hour, to convert the phase of alumina in the shell to the crystallinesapphire phase of alumina. FIG. 4 is a SEM image illustrating thespheres formed from the process.

This is a theoretical example. In Example 2, the polystyrene templatespheres can be placed into a container under vacuum, and sufficientalumoxane solution can be injected into the container so as to submergethe template spheres. The container can be vented, followed by drainingof the alumoxane solution, and drying of the spheres under controlledconditions in a ceramic crucible. The preferred conditions can be atroom temperature for 48 hours under 70% relative humidity. The spherescan be recoated according to this vacuum method two more times and driedunder the preferred conditions to achieve a uniform coating, and tomaximize their sphericity. The alumina spheres can be heat processed at180° C., recoated under vacuum, and dried under the preferredconditions, and sintered at 1200° C., as Example 1.

In Example 3, the Cenosphere template spheres were submerged in thealumoxane solution at room temperature. The solution was then drained,and the spheres placed in a ceramic crucible, which were allowed to dryunder controlled conditions. The preferred conditions were at roomtemperature for 48 hours under 70% relative humidity. These dried,coated spheres were then agitated, and recoated two more times as statedabove to achieve a uniform coating, and to maximize their sphericity.The spheres were then heated to 460° C. for an hour to burn off organicsand to set the alumina shell. After cooling to room temperature, thespheres were coated again with the alumoxane solution, dried, andreheated to 180° C., as stated above, which results in a thickening ofthe alumina shell. The templated alumina spheres were then sintered at1200° C. for 1 hour, to convert the phase of alumina in the shell to thecrystalline sapphire phase of alumina. FIG. 5 is a SEM imageillustrating such spheres formed from the process.

This is a theoretical example. In Example 4, the Cenosphere templatespheres can be placed into a container under vacuum, and sufficientalumoxane solution can be injected into the container so as to submergethe template spheres. The container can be vented, followed by drainingof the alumoxane solution, and drying of the spheres under controlledconditions in a ceramic crucible. The preferred conditions can be atroom temperature for 48 hours under 70% relative humidity. The spherescan be recoated according to this vacuum method two more times and driedunder the preferred conditions to achieve a uniform coating, and tomaximize their sphericity. The alumina spheres can be heat processed at460° C., recoated under vacuum, and dried under the preferredconditions, and sintered at 1200° C., as in Example 3.

This is a theoretical example. In Example 5, spherical Styroporetemplates of 300-1200 micron diameter range and 50-200 micron wallthickness can be infiltrated with the alumoxane solution, ranging from0.5-60 weight percent. The resulting diameter and wall thickness of thealumina shells formed can be dictated by the diameter and wall thicknessof the Styropore templates chosen. The template spheres can be submergedin the solution at room temperature. The solution can then be drained,and the spheres placed in a ceramic crucible, which can be allowed todry under controlled conditions. The preferred conditions can be at roomtemperature for 48 hours under 70% relative humidity. These dried,infiltrated spheres can then be heated to at least 180° C., to calcinethe infiltrated alumoxane nanoparticles to alumina, followed by furtherheating at a ramp rate of 0.2° C./min to 230° C. A hold of 1 hour at230° C. can be allowed for burnoff of the Styropore template, resultingin a porous spherical alumina shell. Further heating at a ramp rate of1° C./min to 500° C. resulted in further setting of the alumina shell.The alumina shells can then be cooled to room temperature, andthemselves infiltrated with the alumoxane solution, as stated above forthe Styropore templates. This can result in filling of the void spaceleft by the lost Styropore template. These infiltrated shells can beheated at a ramp rate of 1° C./min to 500° C., to calcine theinfiltrated alumoxane nanoparticles, and to further set the infiltratedalumina shell, followed by cooling to room temperature. These shells canbe infiltrated and calcined once more, to produce a uniform shell ofmaximal sphericity, followed by sintering at 1200° C. for one hour, toconvert the phase of alumina in the shell to the crystalline sapphirephase of alumina.

This is a theoretical example. In Example 6 the Styropore spheretemplates can be placed into a container under vacuum, and sufficientalumoxane solution can be injected into the container so as to submergethe template spheres. The container can be vented, followed by drainingof the alumoxane solution, and drying of the infiltrated Styroporespheres under controlled conditions in a ceramic crucible. The preferredconditions can be at room temperature for 48 hours under 70% relativehumidity. These dried, infiltrated spheres can then be heated to atleast 180° C., to calcine the infiltrated alumoxane nanoparticles toalumina, followed by further heating at a ramp rate of 0.2° C./min to230° C. A hold of 1 hour at 230° C. can be allowed for burnoff of theStyropore template, resulting in a porous spherical alumina shell.Further heating at a ramp rate of 1° C./min to 500° C. can result infurther setting of the alumina shell. The alumina shells can then becooled to room temperature, and themselves infiltrated under the samevacuum conditions with the alumoxane solution, as stated above for theStyropore templates. This can result in filling of the void space leftby the lost Styropore template. These infiltrated shells can be heatedat a ramp rate of 1° C./min to 500° C., to calcine the infiltratedalumoxane nanoparticles, and to further set the infiltrated aluminashell, followed by cooling to room temperature. These shells can beinfiltrated and calcined once more, to produce a uniform shell ofmaximal sphericity, followed by sintering at 1200° C. for one hour, toconvert the phase of alumina in the shell to the crystalline sapphirephase of alumina.

This is a theoretical example. In Example 7, hollow spherical glasstemplate beads of 150-850 micron size range can be coated with thealumoxane solution, ranging from 0.5-20 weight percent. The templatespheres can be submerged in the solution at room temperature. Thesolution can then be drained, and the spheres placed in a ceramiccrucible, which can be allowed to dry under controlled conditions. Thepreferred conditions can be at room temperature for 48 hours under 70%relative humidity. These dried, coated spheres can then be agitated, andrecoated two more times as stated above to achieve a uniform coating,and to maximize their sphericity. The spheres can then be heated at aramp rate of 1° C./min to 460° C., followed by a hold of 40 minutes toburn off organics and to set the alumina shell. After cooling to roomtemperature, the spheres can be coated again with the alumoxanesolution, dried, and reheated to 460° C., as stated above, whichresulted in a thickening of the alumina shell. The templated aluminaspheres can then be sintered at 1200° C. for 6 hours, which resulted inthe formation of an aluminosilicate at the silica-alumina interface,consisting of mullite and corundum phases. The amorphous silica furthercan serve as a reactive wetting phase to facilitate the resorption ofsome of the alumina, in creating mullite at the interface. The relativeamount of mullite and alumina phases formed can be dependent on theamounts of silica and alumina initially present, and can be calculatedfrom an alumina-silica binary phase diagram. Complete conversion of thesilica phase to mullite can occur in the aluminosilicate sphere, withthe alumina in excess of 60% originally present in the startingmaterial, comprising the alumina phase of the sphere.

This is a theoretical example. In Example 8, a known amount of solid,hollow or porous beads would be fluidized in a fluid bed. An alumoxanesolution would be sprayed into the chamber in order to coat the beads.The beads will then be dried by introducing a heated gas into thechamber or by virtue of their movement through the gaseous “fluid”.Cycles of spraying and drying can be repeated, depending on thethickness of the coating required. Once the desired thickness has beenachieved, the coated beads are removed and sintered to 1200° C. in orderto convert the alumina to sapphire.

This is a theoretical example. In Example 9, a known amount of solid,hollow or porous beads would be fluidized in a fluid bed. A solution ofpartially cross-linked hybrid alumoxane polymer would be sprayed intothe chamber in order to coat the beads. This would be followed byspraying a curing agent into the chamber in order to set the polymercoating. Alternatively, a molten hybrid alumoxane polymer could besprayed onto the chamber to coat the particles. The beads can then becooled by introducing cooled air into the chamber. In the case of apolymer that requires heating for cure, heated air can be introducedinto the chamber.

In Example 10, 440 mL of water was mixed with 20 mL glacial acetic acid,in which 4 g of Catapal B and 36 g Dispal 11N7-80 boehmites werepeptized with mixing, at room temperature for 2 hours. After sufficientmixing, 150 g of an 8% wt solution of the mixture was spray coated in afluidized bed (Vector fluidized bed, model MFL.01) onto 20 g ofcenospheres, and dried at 80° C., at 130 liters per minute airflow.These coated cenospheres were then sintered at 5° C./min to 500° C., andthen to 1400° C. at 10C/min, for 2 hours. FIGS. 6-8 illustrate sinteredmicrostructures of the above formulation.

In Example 11, 440 mL of water was mixed with 20 mL glacial acetic acid,in which 4 g of Catapal B and 36 g Dispal 11N7-80 boehmites werepeptized with mixing, at room temperature for 2 hours. To this mixturewas added 50 mL of a 1% wt. Fe₂O₃ solution (1% Fe₂O₃ by total solidswt), with additional stirring. After sufficient mixing, 150 g of an 8%wt solution of the mixture was spray coated in a fluidized bed (Vectorfluidized bed, model MFL.01) onto 20 g of cenospheres, and dried at 80°C., at 130 liters per minute airflow. These coated cenospheres were thensintered at 5° C./min to 500° C., and then to 1200° C. at 10° C./min,for 2 hours. FIGS. 9-11 illustrate sintered microstructures of the aboveformulation.

Applicants specifically incorporate the entire contents of all citedreferences in this disclosure. Further, when an amount, concentration,or other value or parameter is given as either a range, preferred range,or a list of upper preferable values and lower preferable values, thisis to be understood as specifically disclosing all ranges formed fromany pair of any upper range limit or preferred value and any lower rangelimit or preferred value, regardless of whether ranges are separatelydisclosed. Where a range of numerical values is recited herein, unlessotherwise stated, the range is intended to include the endpointsthereof, and all integers and fractions within the range. It is notintended that the scope of the invention be limited to the specificvalues recited when defining a range.

Other embodiments of the present invention will be apparent to thoseskilled in the art from consideration of the present specification andpractice of the present invention disclosed herein. It is intended thatthe present specification and examples be considered as exemplary onlywith a true scope and spirit of the invention being indicated by thefollowing claims and equivalents thereof.

1. A proppant comprising a template material and a shell on said template material, wherein said shell comprises a ceramic material or oxide thereof or a metal oxide.
 2. The proppant of claim 1, wherein said template material is porous.
 3. The proppant of claim 1, wherein said template material is a hollow sphere.
 4. The proppant of claim 1, wherein said template material is a closed foam network.
 5. The proppant of claim 1, wherein said template material is a non-composite material.
 6. The proppant of claim 1, wherein said template material is a single particle.
 7. The proppant of claim 1, wherein said template material is a cenosphere.
 8. The proppant of claim 1, wherein said template material has a crush strength of 1,000 psi or less.
 9. The proppant of claim 1, wherein said template material has voids.
 10. The proppant of claim 1, wherein said shell is a sintered shell.
 11. The proppant of claim 1, wherein said shell comprises sintered nanoparticles.
 12. The proppant of claim 1, wherein said shell has an average grain size of about 10 microns or less.
 13. The proppant of claim 1, wherein said shell further comprises at least one sintering aid, glassy phase formation agent, grain growth inhibitor, ceramic strengthening agent, crystallization control agent, or phase formation control agent, or any combination thereof.
 14. The proppant of claim 1, wherein said sintering aid, grain growth inhibitor, ceramic strengthening agent, crystallization control agent, or phase formation control agent comprises yttrium, zirconium, iron, magnesium, alumina, bismuth, lanthanum, silicon, calcium, cerium, silicates, borates, or oxides thereof or any combination thereof.
 15. The proppant of claim 13, wherein said sintering aid, grain growth inhibitor, ceramic strengthening agent, glassy phase formation agent, crystallization control agent, or phase formation control agent is present in said shell in an amount of from about 0.1% to about 5% by weight of said shell.
 16. The proppant of claim 1, wherein said template material is a hollow cenosphere.
 17. The proppant of claim 1, wherein said template material comprises fly ash particles or particles derived from fly ash.
 18. The proppant of claim 1, wherein said template material is a hollow spheroidal particle.
 19. The proppant of claim 1, wherein said template material is precipitator fly ash.
 20. The proppant of claim 1, wherein said shell is substantially non-porous.
 21. The proppant of claim 1, wherein said shell is substantially uniform in thickness around the entire outer surface of said template material.
 22. The proppant of claim 1, wherein said shell is a continuous shell around said outer surface of said template material.
 23. The proppant of claim 1, wherein said shell fully encapsulates said template material.
 24. The proppant of claim 1, wherein said shell is a non-reactive coating on said template material.
 25. The proppant of claim 1, wherein said shell chemically bonds to said template material or a portion thereof.
 26. The proppant of claim 1, wherein at least a portion of said shell diffuses, infiltrates, or impregnates a portion of said template material.
 27. The proppant of claim 1, wherein at least a portion of said shell adsorbs or absorbs onto at least a portion of said template material.
 28. The proppant of claim 1, wherein said shell is in direct contact with the outer surface of said template material.
 29. The proppant of claim 1, wherein said proppant has a crush strength of 3,000 psi or greater.
 30. The proppant of claim 1, wherein said proppant has a specific gravity of from 0.6 g/cc to about 2.5 g/cc.
 31. The proppant of claim 1, wherein said shell has a wall thickness of from about 15 to about 120 microns.
 32. The proppant of claim 1, wherein said proppant is spherical and has a sphericity of at least about 0.9.
 33. The proppant of claim 1, wherein said shell is a spray-coated shell.
 34. The proppant of claim 1, wherein said shell comprises at least one alumina, aluminosilicate, aluminate, or silicate.
 35. The proppant of claim 34, wherein said aluminate or silicate or aluminosilicate is an aluminate or silicate or aluminosilicate of calcium, yttrium, magnesium, titanium, lanthanum, barium, silicon, or any combination thereof.
 36. The proppant of claim 1, wherein said template material is a naturally occurring material.
 37. The proppant of claim 1, wherein one or more intermediate coatings are present between said template material and said shell
 38. A method of making the proppant of claim 1, comprising coating said template material with a formulation comprising said ceramic material or oxide thereof or metal oxide to form said shell around said template and then sintering said shell.
 39. The method of claim 38, wherein said sintering occurs at a sintering temperature of from about 800° C. to about 1700° C.
 40. The method of claim 38, wherein said coating of said template material is achieved by spray coating.
 41. The method of claim 38, wherein said shell is a non-alpha aluminum oxide that upon said sintering forms an α-aluminum oxide coating.
 42. The method of claim 38, wherein said formulation is a slurry comprising said ceramic material or oxide thereof or metal oxide, along with a liquid carrier.
 43. The method of claim 38, wherein said formulation is introduced into a spray coating chamber as an atomized spray and said template material is suspended in air during said coating of said template material.
 44. The method of claim 38, wherein said sintering is sufficient to densify said ceramic material or oxide thereof or metal oxide and form a continuous coating.
 45. The method of claim 38, wherein said formulation comprises at least one acid, surfactant, suspension aid, glassy phase formation agent, sintering aid, grain growth inhibitor, ceramic strengthening agent, crystallization control agent, or phase formation control agent, or any combination thereof.
 46. The method of claim 38, wherein said ceramic material or oxide thereof or metal oxide is in the form of nanoparticles.
 47. A proppant formulation comprising the proppant of claim 1 and a carrier.
 48. The proppant formulation of claim 47, wherein said carrier is water or brine.
 49. A method to prop open subterranean formation fractions comprising introducing the proppant formulation of claim 47 into said subterranean formation.
 50. The proppant of claim 1, wherein said proppant has each of the following characteristics: (a) an overall diameter of from about 90 microns to about 1,600 microns; (b) spherical; (c) said shell is substantially non-porous; (d) said proppant has a crush strength of about 3,000 psi or greater; (e) said coating has a wall thickness of from about 15 to about 120 microns; (f) said proppant has a specific gravity of from about 0.9 to about 1.5 g/cc; and (g) said template material is a hollow sphere.
 51. The proppant of claim 50, wherein said template material is a cenosphere.
 52. The proppant of claim 50, wherein said template material is an aluminate.
 53. The proppant of claim 50, wherein said template material is a sintered aluminum oxide.
 54. The proppant of claim 50, wherein said crush strength of said template material alone is less than 1,000 psi.
 55. The proppant of claim 50, wherein said template material is a non-composite material.
 56. The proppant of claim 1, wherein said shell is an α-aluminum oxide coating.
 57. The proppant of claim 1, wherein said proppant has a crush strength of from 5,000 psi to 10,000 psi.
 58. The proppant of claim 1, wherein said shell comprises Mullite, Cordierite, or both.
 59. The method of claim 38, wherein said shell, prior to said sintering, comprises nanoparticles as a mixture of primary particles and agglomerates.
 60. The method of claim 59, wherein said primary particles have an average particle size of from about 1 nm to about 150 nm, and said agglomerates have an average particle size of from about 10 nm to about 350 nm.
 61. The method of claim 38, wherein said formulation is prepared by peptizing Boehmite with at least one acid to form a sol-gel formulation comprising alumoxane.
 62. The method of claim 38, wherein said formulation is a slurry comprising an alumoxane, along with a liquid carrier.
 63. The proppant of claim 58, wherein said sintering aid, grain growth inhibitor, ceramic strengthening agent, glassy phase formation agent, crystallization control agent, or phase formation control agent comprises yttrium, zirconium, iron, magnesium, alumina, bismuth, silicon, lanthanum, calcium, cerium, silicates, borates, or oxides thereof or any combination thereof.
 64. The proppant of claim 1, wherein said template material is a blown sphere.
 65. The proppant formulation of claim 47, wherein said carrier comprises a gel, a foam, a gas, a hydrocarbon, oil, or any combination thereof.
 66. The proppant of claim 1, wherein said shell has an average grain size of 1 micron or less.
 67. The proppant of claim 1, wherein said shell has an average grain size of 0.1 micron to 0.5 micron.
 68. The proppant of claim 67, wherein said shell has a maximum grain size of 1 micron.
 69. The proppant of claim 66, wherein at least 90% of all grain sizes are within the range of from 0.1 to 0.6 micron.
 70. The proppant of claim 1, wherein said proppant has a specific gravity of from 0.9 g/cc to about 1.5 g/cc.
 71. The proppant of claim 1, wherein said proppant has a specific gravity of from 1.0 g/cc to about 1.3 g/cc.
 72. A proppant comprising a surface that comprises a ceramic material or oxide thereof, or a metal oxide, wherein said surface has an average grain size of 1 micron or less.
 73. The proppant of claim 72, wherein said average gain size is about 0.5 micron or less.
 74. The proppant of claim 72, wherein said average grain size is from 0.1 micron to 0.5 micron.
 75. The proppant of claim 72, wherein said surface has a maximum grain size of 1 micron.
 76. The proppant of claim 72, wherein at least 90% of all grain sizes are within the range of from about 0.1 to about 0.6 micron.
 77. The proppant of claim 72, wherein said proppant has a crush strength of 3000 psi or greater.
 78. The proppant of claim 72, wherein said ceramic material is an aluminum oxide.
 79. The proppant of claim 72, wherein said ceramic material or oxide thereof or a metal oxide further contains yttrium, zirconium, iron, magnesium, alumina, bismuth, lanthanum, silicon, calcium, cerium, silicates, borates, or oxides thereof or any combination thereof.
 80. A proppant formulation comprising the proppant of claim 72 and a carrier.
 81. A method to prop open subterranean formation fractions comprising introducing the proppant formulation of claim 80 into said subterranean formation.
 82. The proppant in claim 1, wherein said shell comprises one or more crystalline phases or one or more glassy phases, or combinations thereof.
 83. The proppant of claim 1, wherein said template material is a synthetic ceramic microsphere.
 84. The proppant of claim 83, wherein said template is formed from a blowing process.
 85. The proppant of claim 83, wherein said template is formed from a drop tower process.
 86. A method of treating a subterranean producing zone penetrated by a well bore comprising the steps of: (a) preparing or providing a treating fluid that comprises a hydrocarbon or water carrier fluid having the proppant of claim 1 suspended therein, and (b) pumping said treating fluid into said subterranean producing zone whereby said particles are deposited therein.
 87. The method of claim 86, wherein said treating fluid is a fracturing fluid and said particles are deposited in fractures formed in said subterranean producing zone.
 88. The method of claim 86, wherein said treating fluid is a gravel packing fluid and said particles are deposited in said well bore adjacent to said subterranean producing zone. 